Synthesis and characterization of metathesis catalysts

ABSTRACT

This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals, and pharmaceuticals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a national stage application (under 35 U.S.C. § 371) of PCT/US2017/046283, filed Aug. 10, 2017, which claims benefit of U.S. application Ser. No. 62/378,791, filed Aug. 24, 2016, both of which are incorporated herein by reference in their entirety.

RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application No. 62/378,791, filed Aug. 24, 2016.

TECHNICAL FIELD

This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.

BACKGROUND

Since its discovery in the 1950s, olefin metathesis has emerged as a valuable synthetic method for the formation of carbon-carbon double bonds. Recent advances in applications to organic syntheses and polymer syntheses mostly rely on developments of well-defined olefin metathesis catalysts.

The technology of ruthenium metathesis catalysts has enabled the development of several research platforms including: ring opening metathesis polymerization (ROMP), ring opening cross metathesis (ROCM), cross metathesis (CM), and ring closing metathesis (RCM).

First Generation Grubbs ruthenium olefin metathesis catalysts, such as: (PCy₃)₂(Cl)₂Ru═CHPh, have been largely used in organic synthesis.

The incorporation of certain types of N-Heterocyclic Carbene (NHC) ligands played an essential role in the development of ruthenium metathesis catalysts, giving rise to the Second Generation Grubbs ruthenium olefin metathesis catalysts, such as: (IMesH₂)(PCy₃)(Cl)₂Ru═CHPh, where IMesH₂ is 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene.

In order to exchange the phosphine on the Second Generation Grubbs ruthenium olefin metathesis catalysts, the Grubbs group reported in 2001 (Organometallics 2001, 20, 5314-5318) a method involving a precursor bearing two pyridine ligands: (IMesH₂)(Cl)₂(C₅H₅N)₂Ru═CHPh. The labile pyridine ligands have allowed the preparation of diverse ruthenium olefin metathesis catalysts. However, the preparation of pyridine complexes, requires large quantities of expensive and malodorous reagents (pyridine), and difficult reaction conditions (negative ° C. temperatures) especially for industrial scale-up.

Therefore there is an ongoing need for efficient, high yield, high purity and ease in scaling up procedures for the synthesis of olefin metathesis catalysts, particularly Second Generation Grubbs ruthenium olefin metathesis catalysts.

SUMMARY OF THE INVENTION

To meet this need the inventors have discovered novel ruthenium olefin metathesis catalysts, bearing a sulfoxide ligand as described herein. The ruthenium olefin metathesis catalysts bearing sulfoxide labile ligands exhibit high stability and allow the ready synthesis of various Second Generation Grubbs ruthenium olefin metathesis catalysts in higher yield and with higher purity, compared to the existing procedures.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (I)

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group [—S(O)—];

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene.

In one embodiment, the invention provides a method of synthesizing the olefin metathesis catalysts of the invention.

In one embodiment, the invention provides a method of using the olefin metathesis catalysts of the invention in metathesis reactions.

In one embodiment, the invention provides a method of synthesizing a Second Generation Grubbs catalyst, using an olefin metathesis catalyst of the invention.

Other embodiments of the invention are described herein.

These and other aspects of the present invention will be apparent to one of skill in the art, in light of the following detailed description and examples. Furthermore, it is to be understood that none of the embodiments or examples of the invention described herein are to be interpreted as being limiting.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C747.

FIG. 2 depicts an Oak Ridge Thermal Ellipsoid Plot (ORTEP) diagram of C647_(m).

FIG. 3 shows the conversion of diethyl 2,2-diallylmalonate to 4,4-bis(ethoxy carbonyl)cyclo-pentene in the presence of an array of ruthenium catalysts.

DETAILED DESCRIPTION

Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an olefin” includes a single olefin as well as a combination or mixture of two or more olefins, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group, typically, although not necessarily, containing 1 to 30 carbon atoms, generally, containing 1 to 24 carbon atoms, typically, 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically, having 4 to 8, preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein refers to a divalent linear, branched, or cyclic alkyl group, where “alkyl” is as defined herein.

The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to 30 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, iso-propenyl, n-butenyl, iso-butenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Generally, “alkenyl” groups herein contain 2 to 24 carbon atoms, typically, “alkenyl” groups herein contain 2 to 12 carbon atoms. The term “lower alkenyl” intends an “alkenyl” group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic “alkenyl” group, typically, having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to “alkenyl” substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to “alkenyl” in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing “alkenyl” and lower “alkenyl,” respectively. The term “alkenyl” is used interchangeably with the term “olefin” herein.

The term “alkenylene” as used herein refers to a divalent linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined herein.

The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to 30 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Generally, “alkynyl” groups herein contain 2 to 24 carbon atoms; typical “alkynyl” groups described herein contain 2 to 12 carbon atoms. The term “lower alkynyl” intends an “alkynyl” group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to “alkynyl” substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to “alkynyl” in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing “alkynyl” and lower “alkynyl,” respectively.

The term “alkoxy” as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be represented as —O-alkyl where alkyl is as defined herein. A “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy,” respectively, refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). “Aryl” groups contain 5 to 30 carbon atoms, generally, “aryl” groups contain 5 to 20 carbon atoms; and, typically, “aryl” groups contain 5 to 14 carbon atoms. Exemplary “aryl” groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups; for example 2,4,6-trimethylphenyl (i.e., mesityl or Mes), 2-methyl-phenyl, 2,6-di-iso-propylphenyl (i.e., DIPP or DiPP), 2-isopropyl-phenyl (i.e., IPP, Ipp, or ipp), 2-iso-propyl-6-methylphenyl (i.e., MIPP, Mipp, or MiPP). The terms “heteroatom-containing aryl” and “heteroaryl” refer to “aryl” substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined herein. An “aryloxy” group can be represented as —O-aryl where aryl is as defined herein. Preferred “aryloxy” groups contain 5 to 24 carbon atoms, and particularly preferred “aryloxy” groups contain 5 to 14 carbon atoms. Examples of “aryloxy” groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined herein. “Alkaryl” and “aralkyl” groups contain 6 to 30 carbon atoms; generally, “alkaryl” and “aralkyl” groups contain 6 to 20 carbon atoms; and, typically, “alkaryl” and “aralkyl” groups contain 6 to 16 carbon atoms. “Alkaryl” groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of “aralkyl” groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula —OR wherein R is “alkaryl” or “aralkyl,” respectively, as defined herein.

The term “acyl” refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl,” and “aralkyl” are as defined herein.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that can be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and can be monocyclic, bicyclic, or polycyclic.

The terms “halo,” “halogen,” and “halide” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

The term “hydrocarbyl” refers to univalent “hydrocarbyl” moieties containing 1 to 30 carbon atoms, typically, containing 1 to 24 carbon atoms, specifically containing 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a “hydrocarbyl” group of 1 to 6 carbon atoms, typically, 1 to 4 carbon atoms, and the term “hydrocarbylene” intends a divalent “hydrocarbyl” moiety containing 1 to 30 carbon atoms, typically, 1 to 24 carbon atoms, specifically 1 to 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species. The term “lower hydrocarbylene” intends a “hydrocarbylene” group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to “hydrocarbyl” substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to “hydrocarbylene” substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene” refer to “hydrocarbylene” in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing “hydrocarbyl” and “hydrocarbylene” moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus, or silicon, typically, nitrogen, oxygen, or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and “heteroaromatic,” respectively, refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” can be monocyclic, bicyclic, or polycyclic as described herein with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, it is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—(CO)—X where X is halo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxyl (—COOH), carboxylato (—COO⁻), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CS)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CS)—N(C₅-C₂₄ aryl)₂), carbamido (—NH—(CO)—NH₂), cyano(—C≡N), cyanato (—O—C≡N), thiocyanato (—S—C≡N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, (C₁-C₂₄ alkyl)(C₅-C₂₄ aryl)-substituted amino, (C₂-C₂₄ alkyl)-amido (—NH—(CO)-alkyl), (C₆-C₂₄ aryl)-amido (—NH—(CO)-aryl), imino (—CR═NH where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), (C₂-C₂₀ alkyl)-imino (—CR═N(alkyl), where R is hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R is hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato (—SO₂—O⁻), (C₁-C₂₄ alkyl)-sulfanyl (—S-alkyl; also termed “alkylthio”), (C₅-C₂₄ aryl)-sulfanyl (—S-aryl; also termed “arylthio”), (C₁-C₂₄ alkyl)-sulfinyl (—(SO)-alkyl), (C₅-C₂₄ aryl)-sulfinyl (—(SO)-aryl), (C₁-C₂₄ alkyl)-sulfonyl (—SO₂-alkyl), mono-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(H)alkyl), di-(C₁-C₂₄ alkyl)-aminosulfonyl —SO₂—N(alkyl)₂, (C₅-C₂₄ aryl)-sulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O⁻)₂), phosphinato (—P(O)(O⁻)), phospho (—PO₂), and phosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferably C₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl (preferably C₆-C₁₆ aralkyl).

By “Grubbs-Hoveyda ligands,” it is meant benzylidene ligands having a chelating alkyloxy group attached to the benzene ring at the ortho position.

The term “sulfoxide group” refers to —[S(O)]—.

By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, it is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described herein. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated herein. Analogously, the herein-mentioned hydrocarbyl moieties can be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

“Optional” or “optionally” means that the subsequently described circumstance can or cannot occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent can or cannot be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

Olefin Metathesis Catalysts

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (I):

wherein

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (I), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ and L² are independently neutral electron donor ligands;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (II):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L¹ is a carbene;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X³ and X⁴ are independently O or S; and

R^(x), B^(y), R^(w), and R^(z) are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(x), R^(y), R^(w), and R^(z) are independently hydrogen, halogen, unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen, unsubstituted phenyl, substituted phenyl, or halogen; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (II), wherein:

M is Ru;

L¹ is a carbene;

n is 0;

m is 0;

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X³ and X⁴ are each S; and

R^(x), R^(y), R^(w), and R^(z) are independently hydrogen, halogen, unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen, unsubstituted phenyl, substituted phenyl, or halogen; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (III):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), N, O, S, or P; only one of X or Y can be C or CR^(3a); typically, X and Y are each N;

Q¹, Q², R³, R^(3a) and R⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q¹, Q², R³, R^(3a), and R⁴ are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or —(CO)—; typically, Q¹, Q², R³, R^(3a), and R⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P, or CR^(3a), and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P, or CR^(3a), and q is 2 when X is C.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (III), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F; and

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), N, O, S, or P; only one of X or Y can be C or CR^(3a); typically, X and Y are each N;

Q¹, Q², R³, R^(3a) and R⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, Q¹, Q², R³, R^(3a), and R⁴ are optionally linked to X or Y via a linker such as unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, or —(CO)—; typically, Q¹, Q², R³, R^(3a), and R⁴ are directly linked to X or Y; and

p is 0 when X is O or S, p is 1 when X is N, P, or CR^(3a), and p is 2 when X is C; q is 0 when Y is O or S, q is 1 when Y is N, P, or CR^(3a), and q is 2 when X is C.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV):

wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1;

m is 0, 1, or 2;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; and only one of X or Y can be C or CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

“s” and “t” are independently 1 or 2;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl.

In one embodiment of Formula (IV), any two or more of X¹, X², L², R¹, and R² are optionally linked together to form a cyclic group, including bidentate or multidentate ligands; or any one or more of X¹, X², L², R¹, and R² is/are optionally attached to a support.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV):

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; only one of X or Y can be C or CR^(3a); typically, X and Y are each N;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a linker, typically, unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; generally, Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—; typically, Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, wherein R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl; “s” and “t” are independently 1 or 2; typically, “s” and “t” are each 1; or any two of R¹¹, R¹², R¹³, and R¹⁴ are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, 2-fluoro-6-methylphenyl, or 2-methyl-phenyl; or when X is CR^(3a), then R^(3a) and R⁴ can form together a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently anionic ligands; generally, X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are independently C, CR^(3a), or N; only one of X or Y can be C or CR^(3a); typically, X and Y are each N;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a linker, typically, unsubstituted hydrocarbylene, substituted hydrocarbylene, unsubstituted heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; generally, Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—; typically, Q is —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹¹, R¹², R¹³ and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl; “s” and “t” are independently 1 or 2; typically, “s” and “t” are each 1; or any two of R¹¹, R¹², R¹³, and R¹⁴ are optionally linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2-iso-propyl-phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst, represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are each N;

Q is —(CH₂—CH₂)— (i.e., a two-atom linkage having the structure —[CR¹¹R¹²]_(s)[CR¹³R¹⁴]_(t)—; wherein R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen; and “s” and “t” are each 1);

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide.

Therefore, the olefin metathesis catalyst of Formula (IV) can also be represented by the structure of Formula (V):

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from C₁-C₂₀ alkyl, substituted unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; and

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl;

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl; or IV and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are each Cl; and

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl (i.e.,

or 2-methyl-1-propenyl (i.e., —CH═C(CH₃)₂ or

or R¹ and R² are linked together to form 3-phenylinden-1-ylidene (i.e.,

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹ and X² are each Cl;

R³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl, 2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl; and

R⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenylinden-1-ylidene;

R^(a) and R^(b) are linked together to form with the sulfoxide group a tetrahydrothiophene oxide;

X¹ and X² are each Cl;

R³ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, adamantyl, 2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl; and

R⁴ is phenyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-methyl-phenyl, or 2-isopropyl-6-methyl phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (V), wherein:

R¹ and R² are linked together to form 3-phenylinden-1-ylidene;

R^(a) is methyl;

R^(b) is methyl;

X¹ and X² are each Cl;

R³ is 2,4,6-trimethylphenyl; and

R⁴ is 2,4,6-trimethylphenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (V) are described in Table (1), wherein X¹ is Cl and X² is Cl.

TABLE 1 Catalyst R¹ R² R³ R⁴ R^(a) R^(b)  1 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  2 H Ph Mes Mes Me Me  3 H Ph Mipp Mipp Me Me  4 H Ph adamantyl Mes Me Me  5 H Ph DIPP DIPP Me Me  6 H Ph IPP IPP Me Me  7 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  8 H

Mes Mes Me Me  9 H

Mipp Mipp Me Me 10 H

adamantyl Mes Me Me 11 H

DIPP DIPP Me Me 12 H

IPP IPP Me Me 13 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 14 H

Mes Mes Me Me 15 H

Mipp Mipp Me Me 16 H

adamantyl Mes Me Me 17 H

DIPP DIPP Me Me 18 H

IPP IPP Me Me 19

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me 20

Mes Mes Me Me 21

Mipp Mipp Me Me 22

adamantyl Mes Me Me 23

DIPP DIPP Me Me 24

IPP IPP Me Me 25 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

26 H Ph Mes Mes

27 H Ph Mipp Mipp

28 H Ph adamantyl Mes

29 H Ph DIPP DIPP

30 H Ph IPP IPP

31 H

2-Me—C₆H₅ 2-Me—C₆H₅

32 H

Mes Mes

33 H

Mipp Mipp

34 H

adamantyl Mes

35 H

DIPP DIPP

36 H

IPP IPP

37 H

2-Me—C₆H₅ 2-Me—C₆H₅

38 H

Mes Mes

39 H

Mipp Mipp

40 H

adamantyl Mes

41 H

DIPP DIPP

42 H

IPP IPP

43

2-Me—C₆H₅ 2-Me—C₆H₅

44

Mes Mes

45

Mipp Mipp

46

adamantyl Mes

47

DIPP DIPP

48

IPP IPP

49 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 50 H Ph Mes Mes n-Bu n-Bu 51 H Ph Mipp Mipp n-Bu n-Bu 52 H Ph adamantyl Mes n-Bu n-Bu 53 H Ph DIPP DIPP n-Bu n-Bu 54 H Ph IPP IPP n-Bu n-Bu 55 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 56 H

Mes Mes n-Bu n-Bu 57 H

Mipp Mipp n-Bu n-Bu 58 H

adamantyl Mes n-Bu n-Bu 59 H

DIPP DIPP n-Bu n-Bu 60 H

IPP IPP n-Bu n-Bu 61 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 62 H

Mes Mes n-Bu n-Bu 63 H

Mipp Mipp n-Bu n-Bu 64 H

adamantyl Mes n-Bu n-Bu 65 H

DIPP DIPP n-Bu n-Bu 66 H

IPP IPP n-Bu n-Bu 67

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 68

Mes Mes n-Bu n-Bu 69

Mipp Mipp n-Bu n-Bu 70

adamantyl Mes n-Bu n-Bu 71

DIPP DIPP n-Bu n-Bu 72

IPP IPP n-Bu n-Bu wherein: Mes is

Mipp is

DIPP is

adamantyl is

IPP is

2-Me-C₆H₅ is

Me is methyl, n-Bu is butyl [CH₃—(CH₂)₃—], Ph is phenyl, and

is [(CH₂)₄—].

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

X and Y are each N;

Q is —(CH═CH)— (i.e., a two-atom linkage having the structure —[CR¹¹═CR¹³]—; wherein R¹¹ and R¹³ are hydrogen);

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide.

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VI):

wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2-iso-propyl-phenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (VI), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenylinden-1-ylidene;

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹ and X² are each Cl; and

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (VI), wherein:

R¹ is hydrogen;

R² is unsubstituted phenyl, substituted phenyl or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl; and

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, or 2-methyl-phenyl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VI) are described in Table (2), wherein X¹ is Cl and X² is Cl.

TABLE 2 Catalyst R¹ R² R³ R⁴ R^(a) R^(b)  73 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  74 H Ph Mes Mes Me Me  75 H Ph Mipp Mipp Me Me  76 H Ph adamantyl Mes Me Me  77 H Ph DIPP DIPP Me Me  78 H Ph IPP IPP Me Me  79 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  80 H

Mes Mes Me Me  81 H

Mipp Mipp Me Me  82 H

adamantyl Mes Me Me  83 H

DIPP DIPP Me Me  84 H

IPP IPP Me Me  85 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  86 H

Mes Mes Me Me  87 H

Mipp Mipp Me Me  88 H

adamantyl Mes Me Me  89 H

DIPP DIPP Me Me  90 H

IPP IPP Me Me  91

2-Me—C₆H₅ 2-Me—C₆H₅ Me Me  92

Mes Mes Me Me  93

Mipp Mipp Me Me  94

adamantyl Mes Me Me  95

DIPP DIPP Me Me  96

IPP IPP Me Me  97 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅

 98 H Ph Mes Mes

 99 H Ph Mipp Mipp

100 H Ph adamantyl Mes

101 H Ph DIPP DIPP

102 H Ph IPP IPP

103 H

2-Me—C₆H₅ 2-Me—C₆H₅

104 H

Mes Mes

105 H

Mipp Mipp

106 H

adamantyl Mes

107 H

DIPP DIPP

108 H

IPP IPP

109 H

2-Me—C₆H₅ 2-Me—C₆H₅

110 H

Mes Mes

111 H

Mipp Mipp

112 H

adamantyl Mes

113 H

DIPP DIPP

114 H

IPP IPP

115

2-Me—C₆H₅ 2-Me—C₆H₅

116

Mes Mes

117

Mipp Mipp

118

adamantyl Mes

119

DIPP DIPP

120

IPP IPP

121 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 122 H Ph Mes Mes n-Bu n-Bu 123 H Ph Mipp Mipp n-Bu n-Bu 124 H Ph adamantyl Mes n-Bu n-Bu 125 H Ph DIPP DIPP n-Bu n-Bu 126 H Ph IPP IPP n-Bu n-Bu 127 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 128 H

Mes Mes n-Bu n-Bu 129 H

Mipp Mipp n-Bu n-Bu 130 H

adamantyl Mes n-Bu n-Bu 131 H

DIPP DIPP n-Bu n-Bu 132 H

IPP IPP n-Bu n-Bu 133 H

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 134 H

Mes Mes n-Bu n-Bu 135 H

Mipp Mipp n-Bu n-Bu 136 H

adamantyl Mes n-Bu n-Bu 137 H

DIPP DIPP n-Bu n-Bu 138 H

IPP IPP n-Bu n-Bu 139

2-Me—C₆H₅ 2-Me—C₆H₅ n-Bu n-Bu 140

Mes Mes n-Bu n-Bu 141

Mipp Mipp n-Bu n-Bu 142

adamantyl Mes n-Bu n-Bu 143

DIPP DIPP n-Bu n-Bu 144

IPP IPP n-Bu n-Bu

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (IV), wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; typically, X¹ and X² are independently Cl, Br, I, or F;

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

Y is N;

X is CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R^(3a) and R⁴ can form together a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—; wherein R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, unsubstituted C₅-C₁₄ aryl, or substituted C₅-C₁₄ aryl; “s” and “t” are each 1;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; and

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted (C₅-C₂₄ aryl), or (C₅-C₂₄ aryl) substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; or R^(3a) and R⁴ can form together a five to ten membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached.

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VII):

wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, or 2-methyl-phenyl;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl, or substituted C₆-C₂₄ heteroaralkyl; typically, R¹¹ and R¹² are each methyl and R¹³ and R¹⁴ are each hydrogen;

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(3a) is unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl, or substituted C₆-C₂₄ heteroaralkyl; typically, R^(3a) is methyl, ethyl, n-propyl, or phenyl; and

R⁴ is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, unsubstituted C₄-C₁₂ cycloalkyl, substituted C₄-C₁₂ cycloalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ heteroaralkyl, or substituted C₆-C₂₄ heteroaralkyl; typically, R⁴ is methyl, ethyl, n-propyl, or phenyl; or R⁴ together with R^(3a) can form a five- to ten-membered cycloalkyl or heterocyclic ring, with the carbon atom to which they are attached.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (VII), wherein:

R¹ is hydrogen;

R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenylinden-1-ylidene;

R^(a) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

R^(b) is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, or phenyl;

X¹ and X² are each Cl; and

R³ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-phenyl, 2-iso-propyl-6-methylphenyl, 2,6-di-ethylphenyl, 2-methyl-6-tert-butylphenyl, 2-ethyl-6-methylphenyl, or 2-methyl-phenyl;

R¹¹ and R¹² are each methyl;

R¹³ and R¹⁴ are each hydrogen;

R^(3a) is methyl, ethyl, n-propyl, or phenyl; and

R⁴ is methyl, ethyl, n-propyl, or phenyl; or R^(3a) and R⁴ form together a five-, six-, or ten-membered cycloalkyl or heterocycle ring, with the carbon atom to which they are attached.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VII) are described in Table (3), wherein X¹ is Cl, X² is Cl, R¹¹ is methyl, R¹² is methyl, R¹³ is hydrogen, and R¹⁴ is hydrogen.

TABLE 3 Catalyst R¹ R² R^(a) R^(b) R³ R^(3a) R⁴ 145 H Ph Me Me 2-Me—C₆H₅ Me Me 146 H Ph Me Me Mes Me Me 147 H Ph Me Me Mipp Me Me 148 H Ph Me Me EMP Me Me 149 H Ph Me Me DIPP Me Me 150 H Ph Me Me IPP Me Me 151 H

Me Me 2-Me—C₆H₅ Me Me 152 H

Me Me Mes Me Me 153 H

Me Me Mipp Me Me 154 H

Me Me EMP Me Me 155 H

Me Me DIPP Me Me 156 H

Me Me IPP Me Me 157 H

Me Me 2-Me—C₆H₅ Me Me 158 H

Me Me Mes Me Me 159 H

Me Me Mipp Me Me 160 H

Me Me EMP Me Me 161 H

Me Me DIPP Me Me 162 H

Me Me IPP Me Me 163

Me Me 2-Me—C₆H₅ Me Me 164

Me Me Mes Me Me 165

Me Me Mipp Me Me 166

Me Me EMP Me Me 167

Me Me DIPP Me Me 168

Me Me IPP Me Me 169 H Ph

2-Me—C₆H₅ Me Me 170 H Ph

Mes Me Me 171 H Ph

Mipp Me Me 172 H Ph

EMP Me Me 173 H Ph

DIPP Me Me 174 H Ph

IPP Me Me 175 H

2-Me—C₆H₅ Me Me 176 H

Mes Me Me 177 H

Mipp Me Me 178 H

EMP Me Me 179 H

DIPP Me Me 180 H

IPP Me Me 181 H

2-Me—C₆H₅ Me Me 182 H

Mes Me Me 183 H

Mipp Me Me 184 H

EMP Me Me 185 H

DIPP Me Me 186 H

IPP Me Me 187

2-Me—C₆H₅ Me Me 188

Mes Me Me 189

Mipp Me Me 190

EMP Me Me 191

DIPP Me Me 192

IPP Me Me 193 H Ph n-Bu n-Bu 2-Me—C₆H₅ Me Me 194 H Ph n-Bu n-Bu Mes Me Me 195 H Ph n-Bu n-Bu Mipp Me Me 196 H Ph n-Bu n-Bu EMP Me Me 197 H Ph n-Bu n-Bu DIPP Me Me 198 H Ph n-Bu n-Bu IPP Me Me 199 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 200 H

n-Bu n-Bu Mes Me Me 201 H

n-Bu n-Bu Mipp Me Me 202 H

n-Bu n-Bu EMP Me Me 203 H

n-Bu n-Bu DIPP Me Me 204 H

n-Bu n-Bu IPP Me Me 205 H

n-Bu n-Bu 2-Me—C₆H₅ Me Me 206 H

n-Bu n-Bu Mes Me Me 207 H

n-Bu n-Bu Mipp Me Me 208 H

n-Bu n-Bu EMP Me Me 209 H

n-Bu n-Bu DIPP Me Me 210 H

n-Bu n-Bu IPP Me Me 211

n-Bu n-Bu 2-Me—C₆H₅ Me Me 212

n-Bu n-Bu Mes Me Me 213

n-Bu n-Bu Mipp Me Me 214

n-Bu n-Bu EMP Me Me 215

n-Bu n-Bu DIPP Me Me 216

n-Bu n-Bu IPP Me Me wherein EMP is

In another embodiment of Formula (IV), the invention provides an olefin metathesis catalyst wherein:

M is a Group 8 transition metal; generally, M is ruthenium or osmium; typically, M is ruthenium;

L² is a neutral electron donor ligand;

n is 0 or 1; typically, n is 0;

m is 0, 1, or 2; typically, m is 0;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X and Y are independently C, CR^(3a), or N; and only one of X or Y can be C or CR^(3a);

R^(3a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)— or [CR¹¹═CR¹³]—;

R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

“s” and “t” are independently 1 or 2;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R¹ and R² are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

the moiety

X³ and X⁴ are independently O or S; and

R^(x), R^(y), R^(w), and R^(z) are independently hydrogen, halogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In another embodiment of Formula (IV), the invention provides an olefin metathesis catalyst wherein:

M is Ru;

n is 0;

m is 0;

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

X and Y are each N;

Q is a two-atom linkage having the structure —[CR¹¹R¹²]_(s)—[CR¹³R¹⁴]_(t)—;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl or hydrogen; generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen, and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ are each hydrogen;

“s” and “t” are each 1;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

the moiety

X³ and X⁴ are each S; and

R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen, halogen, unsubstituted phenyl, or substituted phenyl; generally, R^(x) is methyl, hydrogen, or Cl, R^(y) is hydrogen, R^(w) is hydrogen, and R^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Therefore, the olefin metathesis catalyst of Formula (IV), can also be represented by the structure of Formula (VIII):

wherein:

R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, C₅-C₂₄ aryl substituted with up to three substituents selected from unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 2,6-difluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R¹¹, R¹², R¹³, and R¹⁴ are independently C₁-C₆ alkyl or hydrogen; generally, R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen, and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ are independently hydrogen;

R^(x), R^(y), R^(w), and R^(z) are independently C₁-C₆ alkyl, hydrogen, halogen, unsubstituted phenyl, or substituted phenyl; generally, R^(x) is methyl, hydrogen or Cl, R^(y) is hydrogen, R^(w) is hydrogen, and R^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

In one embodiment, the invention provides an olefin metathesis catalyst represented by the structure of Formula (VIII), wherein:

R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group;

R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, or 2-methyl-phenyl;

R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-methyl-6-tert-butylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, 2,6-di-ethylphenyl, 2-ethyl-6-methylphenyl, 2,4,6-trifluorophenyl, 3,5-di-tert-butylphenyl, 2,4-dimethylphenyl, 2,6-difluorophenyl, or 2-methyl-phenyl;

R¹ is hydrogen and R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene;

R¹¹ is hydrogen or methyl, R¹² is hydrogen or methyl, R¹³ is hydrogen, and R¹⁴ is hydrogen; typically, R¹¹, R¹², R¹³, and R¹⁴ are each hydrogen;

R^(x) is methyl, hydrogen, or Cl, R^(y) is hydrogen, R^(w) is hydrogen, and R^(z) is Cl, t-butyl, hydrogen, or phenyl; or R^(x) and R^(y) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(w) and R^(z) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl; or R^(y) and R^(w) are linked together to form an unsubstituted bicyclic or polycyclic aryl or a substituted bicyclic or polycyclic aryl.

Non-limiting examples of olefin metathesis catalysts represented by the structure of Formula (VIII) are described in Table (4), wherein R^(a) is methyl, R^(b) is methyl, R¹¹ is hydrogen, R¹² is hydrogen, R¹³ is hydrogen, R¹⁴ is hydrogen, R^(y) is hydrogen, and R^(w) is hydrogen.

TABLE 4 Catalyst R¹ R² R³ R⁴ R^(x) R^(z) 217 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 218 H Ph Mes Mes Cl Cl 219 H Ph Mipp Mipp Cl Cl 220 H Ph DIPP DIPP Cl Cl 221 H Ph IPP IPP Cl Cl 222 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 223 H

Mes Mes Cl Cl 224 H

Mipp Mipp Cl Cl 225 H

DIPP DIPP Cl Cl 226 H

IPP IPP Cl Cl 227 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 228 H

Mes Mes Cl Cl 229 H

Mipp Mipp Cl Cl 230 H

DIPP DIPP Cl Cl 231 H

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 232 H

Mes Mes Cl Cl 233 H

Mipp Mipp Cl Cl 234 H

DIPP DIPP Cl Cl 235 H

IPP IPP Cl Cl 236 H

IPP IPP Cl Cl 237

2-Me—C₆H₅ 2-Me—C₆H₅ Cl Cl 238

Mes Mes Cl Cl 239

Mipp Me Cl Cl 240

DIPP DIPP Cl Cl 241

IPP Me Cl Cl 242 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 243 H Ph Mes Mes H Ph 244 H Ph Mipp Mipp H Ph 245 H Ph DIPP DIPP H Ph 246 H Ph IPP IPP H Ph 247 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 248 H

Mes Mes H Ph 249 H

Mipp Mipp H Ph 250 H

DIPP DIPP H Ph 251 H

IPP IPP H Ph 252 H

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 253 H

Mes Mes H Ph 254 H

Mipp Mipp H Ph 255 H

DIPP DIPP H Ph 256 H

IPP IPP H Ph 257

2-Me—C₆H₅ 2-Me—C₆H₅ H Ph 258

Mes Mes H Ph 259

Mipp Mipp H Ph 260

DIPP DIPP H Ph 261

IPP IPP H Ph 262 H Ph 2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 263 H Ph Mes Mes Me t-Bu 264 H Ph Mipp Mipp Me t-Bu 265 H Ph DIPP DIPP Me t-Bu 266 H Ph IPP IPP Me t-Bu 267 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 268 H

Mes Mes Me t-Bu 269 H

Mipp Mipp Me t-Bu 270 H

DIPP DIPP Me t-Bu 271 H

IPP IPP Me t-Bu 272 H

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 273 H

Mes Mes Me t-Bu 274 H

Mipp Mipp Me t-Bu 275 H

DIPP DIPP Me t-Bu 276 H

IPP IPP Me t-Bu 277

2-Me—C₆H₅ 2-Me—C₆H₅ Me t-Bu 278

Mes Mes Me t-Bu 279

Mipp Mipp Me t-Bu 280

DIPP DIPP Me t-Bu 281

IPP IPP Me t-Bu

The present invention also concerns processes for synthesizing the olefin metathesis catalysts of the invention. The olefin metathesis catalysts according to the invention can be prepared analogously to conventional methods as understood by the person skilled in the art of synthetic organic chemistry. For example, synthetic Scheme 1, set forth below, illustrates how the compounds according to the invention can be made.

In a typical procedure, an olefin metathesis catalyst of general Formula (A) is reacted at room temperature with tosyl chloride (TsCl) and an excess of sulfoxide derivative (R^(a)R^(b)SO) to produce an olefin metathesis catalyst of general Formula (V), wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; typically, R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenyl-1-indenylidene;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; and

R^(j), R^(t), and R^(o) are each independently substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ aryl, substituted C₁-C₁₀ alkyl, or unsubstituted C₁-C₁₀ alkyl; generally, R¹, R^(t), and R^(o) are each independently unsubstituted C₅-C₂₄ aryl; typically, R^(j), R^(t), and R^(o) are each phenyl.

In another embodiment, the invention concerns methods of using the olefin metathesis catalysts of the invention in the synthesis of related olefin metathesis catalysts. The ruthenium olefin metathesis catalysts bearing sulfoxide labile ligands of the invention are excellent precursors for various Second Generation Grubbs ruthenium olefin metathesis catalysts. The Second Generation Grubbs ruthenium olefin metathesis catalysts synthesized during these procedures are obtained in higher yield and with higher purity, which presents an advantage compared to the existing synthetic procedures.

For example, synthetic Scheme 2, set forth below, illustrates how olefin metathesis catalysts of Formula (F) can be synthesizing from an olefin metathesis catalyst of Formula (IV):

In a typical procedure, as shown in Scheme 2, the sulfoxide ligand of the olefin metathesis catalyst represented by Formula (IV) can be exchanged with “L” ligand, which is a neutral electron donor. R¹, R², R³, R⁴, R, X¹, X², M, Q, n, m, R^(a), R^(b), and L² are as defined herein. “L” is selected from the group consisting of sulphonated phosphine, phosphite, phosphinite, phosphonite, ether, amine, carbonyl, nitrosyl, pyridine, thioether, Grubbs-Hoveyda ligands, trimethylphosphine (PMe₃), triethylphosphine (PEt₃), tri-n-butylphosphine (PBu₃), tri(ortho-tolyl)phosphine (P-o-tolyl₃), tri-tert-butylphosphine (P-tert-Bu₃), tricyclopentylphosphine (PCp₃), tricyclohexylphosphine (PCy₃), triisopropylphosphine (P-i-Pr₃), trioctylphosphine (POct₃), triisobutylphosphine, (P-i-Bu₃), triphenylphosphine (PPh₃), tri(pentafluorophenyl)phosphine (P(C₆F₅)₃), methyldiphenylphosphine (PMePh₂), dimethylphenylphosphine (PMe₂Ph), diethylphenylphosphine (PEt₂Ph), phosphabicycloalkane (e.g., monosubstituted 9-phosphabicyclo-[3.3.1]nonane, monosubstituted 9-phosphabicyclo[4.2.1]nonane, cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban), pyridine, 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-di-iso-propylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, carbazole, sulfur-containing heterocycles (e.g., thiophene, 1,2-dithiole, 1,3-dithiole, thiepine, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, thioanthrene), oxygen-containing heterocycles (e.g. 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, dibenzofuran), mixed (e.g., isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine), aromatic nitrogen-containing and oxygen-containing heterocycles, monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents.

The ligand exchange reactions are carried out under inert atmosphere (under nitrogen or argon). The reactions generally, are carried out at room temperature or at temperatures from 15° C. to 25° C. or from 25° C. to 60° C., or from 35° C. to 50° C., or from 20° C. to 25° C., or from 30° C. to 40° C., or from 25° C. to 45° C. The reaction times vary from several minutes to several hours 12 hours, 24 hours, or 48 hours. Generally, the reactions take place in solvents such as tetrahydrofuran (THF), benzene, toluene, xylene, diethyl ether, dioxane, alcohols, methyl-tetrahydrofuran, acetone, ethyl acetate, methyl tert-butyl ether (MTBE), dimethylformamide (DMF), and dichloromethane.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (B) starting with an olefin metathesis catalyst of Formula (V):

In a typical procedure, as shown in Scheme 3, the sulfoxide ligand of the olefin metathesis catalyst represented by Formula (V) is exchanged with a PR^(d)R^(e)OR^(f) ligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; typically, R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenyl-1-indenylidene;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(d) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, Rd is unsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, Rd is phenyl;

R^(e) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, Re is unsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, Re is phenyl; and

R^(f) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(f) is unsubstituted C₁-C₁₀ alkyl, unsubstituted C₆-C₁₀ aryl, or unsubstituted C₆-C₁₀ aryl; typically, R^(f) is phenyl, methyl, p-(OMe)phenyl, iso-propyl, or ethyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (C) starting with an olefin metathesis catalyst of Formula (V):

In a typical procedure, as shown in Scheme 4, the sulfoxide ligand of the olefin metathesis catalyst represented by Formula (V) can be exchanged with a PR^(g)OR^(h)OR^(i) ligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; typically, R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(g) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(g) is unsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, R^(g) is phenyl;

R^(h) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(h) is unsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, R^(h) is phenyl or methyl; and

R^(i) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R′ is unsubstituted C₁-C₁₀ alkyl or unsubstituted C₆-C₁₀ aryl; typically, R′ is phenyl or methyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (D) starting with an olefin metathesis catalyst of Formula (V):

In a typical procedure as shown in Scheme 5, the sulfoxide ligand of the olefin metathesis catalyst represented by Formula (V) is exchanged with a Grubbs-Hoveyda ligand at 60° C. in ethyl acetate, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; typically, R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or IV and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, IV and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R^(k) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R^(k) is hydrogen;

R^(l) is hydrogen, halogen, —NO₂, —CN, —CF₃, SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R^(l) is hydrogen;

R^(m) is hydrogen, halogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R^(m) is hydrogen, —NO₂, —CN, —CF₃, —SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, or —NHC(O)OtBu; preferably, R^(m) is hydrogen;

R^(n) is hydrogen, halogen, —NO₂, —CN, —CF₃, SO₂NR^(s) ₂, —NHC(O)CF₃, —NHC(O)C₆F₅, —NHC(O)OtBu, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; typically, R^(a) is hydrogen;

R^(s) is hydrogen or C₁-C₆ alkyl; typically, R^(s) is hydrogen, methyl, ethyl, or n-propyl; and

R^(q) is unsubstituted hydrocarbyl or substituted hydrocarbyl; generally, R^(q) is C₁-C₁₀ alkyl; typically, R^(q) is iso-propyl.

In another embodiment, the invention concerns also processes for synthesizing olefin metathesis catalysts of Formula (E) starting with an olefin metathesis catalyst of Formula (V).

In a typical procedure, as shown in Scheme 6, the sulfoxide ligand of the olefin metathesis catalyst represented by Formula (V) can be exchanged with a P(R^(q))₃ ligand at room temperature in an inert solvent, such as dichloromethane or toluene, wherein:

R¹ is hydrogen;

R² is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R² is unsubstituted phenyl, substituted phenyl, or substituted 1-propenyl; or R¹ and R² are linked together to form an optionally substituted indenylidene; typically, R² is phenyl, 2-iso-propoxy-phenyl, or 2-methyl-1-propenyl; or R¹ and R² are linked together to form 3-phenyl-1-indenylidene;

R^(a) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(a) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(a) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl;

R^(b) is hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R^(b) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or substituted C₅-C₂₄ aryl; typically, R^(b) is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, cyclohexyl, or phenyl; or R^(a) and R^(b) are linked together to form a five or a six heterocyclic membered ring with the sulfoxide group; typically, R^(a) and R^(b) are linked together to form a tetrahydrothiophene oxide;

X¹ and X² are independently halogen, trifluoroacetate, per-fluorophenolate, thiolate, alkylthio, arylthio, or nitrate; generally, X¹ and X² are independently Cl, Br, I, or F; typically, X¹ and X² are each Cl;

R³ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R³ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R³ is adamantyl, 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl;

R⁴ is unsubstituted hydrocarbyl, substituted hydrocarbyl, unsubstituted heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; generally, R⁴ is unsubstituted C₃-C₁₀ cycloalkyl, substituted C₃-C₁₀ cycloalkyl, unsubstituted C₅-C₂₄ aryl, or C₅-C₂₄ aryl substituted with up to three substituents selected from: unsubstituted C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, unsubstituted C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, unsubstituted C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, unsubstituted C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, unsubstituted C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, unsubstituted C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, and halide; typically, R⁴ is 2,4,6-trimethylphenyl, 2,6-di-iso-propylphenyl, 2-iso-propyl-6-methylphenyl, 2-iso-propyl-phenyl, or 2-methyl-phenyl; and

R^(p) is unsubstituted C₁-C₁₀ alkyl, substituted C₁-C₁₀ alkyl, substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; generally, R^(p) is substituted C₆-C₁₀ aryl, unsubstituted C₆-C₁₀ aryl, substituted C₃-C₈ cycloalkyl, or unsubstituted C₃-C₈ cycloalkyl; typically, R^(p) is phenyl, cyclohexyl, or cyclopentyl.

At this stage, those skilled in the art will appreciate that many additional compounds that fall under the scope of the invention can be prepared by performing various common chemical reactions. Details of certain specific chemical transformations are provided in the examples.

The metal carbene olefin metathesis catalysts can be utilized in olefin metathesis reactions according to techniques known in the art. For example, the metal carbene olefin metathesis catalysts are typically added to a resin composition as a solid, a solution, or as a suspension. When the metal carbene olefin metathesis catalysts are added to a resin composition as a suspension, the metal carbene olefin metathesis catalysts are suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, tri-iso-propylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), and which is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction. It will be appreciated that the amount of catalyst that is used (i.e., the “catalyst loading”) in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading can be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate (e.g., cyclic olefins).

Cyclic Olefins

Resin compositions that may be used with the present invention disclosed herein comprise one or more cyclic olefins. Such cyclic olefins may be optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄ hydrocarbons that may be mono-, di-, or poly-cyclic. The cyclic olefin may generally be any strained or unstrained cyclic olefin, provided the cyclic olefin is able to participate in a ROMP reaction either individually or as part of a ROMP cyclic olefin composition.

Examples of bicyclic and polycyclic olefins thus include, without limitation, dicyclopentadiene (DCPD); trimer and other higher order oligomers of cyclopentadiene including without limitation tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer, and cyclopentadiene pentamer; ethylidenenorbornene; dicyclohexadiene; norbornene; C₂-C₁₂ hydrocarbyl substituted norbornenes; 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene; 5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; 5-butenyl-2-norbornene; 5-tolyl-norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenyl norbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyoxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; bicyclo[2.2.1]hept-2-ene-2-carboxylic acid, 2-ethylhexyl ester; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclo-hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxy carbonylnorbornene; endo,endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyl tetracyclododecene; 8-ethyltetracyclododecene; 8-methoxy carbonyltetracyclo dodecene; 8-methyl-8-tetra cyclododecene; 8-cyanotetracyclo dodecene; pentacyclopentadecene; pentacyclo hexadecene; bicyclo[2.2.1]hept-2-ene-5-phenoxymethyl; 2-ethylhexyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; 2-hydroxyethyl ester-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid; bicyclo[2.2.1]hept-5-ene-2-methanol; bicyclo[2.2.1]hept-5-ene-2-heptanoic acid-methyl ester; bicyclo[2.2.1]hept-5-ene-2-hexanoic acid-methyl ester; 1,4:5,8-dimethanonaphthalene, 2-hexyl-1,2,3,4,4a,5,8,8a-octahydro; bicyclo[2.2.1]hept-5-ene-2-octanoic acid-methyl ester; 1,4:5,8-dimethano naphthalene; 2-butyl-1,2,3,4,4a,5,8,8a-octahydro; ethylidenetetracyclododecene; 2-vinyl-1,2,3,4,4a,5,8,8a-octahydro-1,4:5,8-dimethano naphthalene; and the like, and their structural isomers, stereoisomers, and mixtures thereof.

EXPERIMENTAL General Information—Materials and Methods

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. The examples are to be considered as not being limiting of the invention described herein. Surprisingly, the olefin metathesis catalysts of the invention were obtained only in the cis configuration, no traces of the trans stereoisomers were detected.

All reactions involving metal complexes were conducted in oven-dried glassware under an argon or nitrogen atmosphere using standard Schlenk techniques. Chemicals and solvents were obtained from Sigma-Aldrich, Strem, Alfa Aesar, Nexeo, Brenntag, A G Layne and TCI. Commercially available reagents were used as received unless otherwise noted. Silica gel was purchased from Fisher (0.040-0.063 μm, EMD Millipore).

The crystallographic measurements were performed at 100(2) K using a Bruker APEXII CCD area detector diffractometer (Mo-K_(α) radiation, λ=0.71073 Å). In each case, a specimen of suitable size and quality was selected and mounted onto a nylon loop. The structures were solved by direct methods, which successfully located most of the non-hydrogen atoms. Semi-empirical absorption corrections were applied. Subsequent refinement on F² using the SHELXTL/PC package (version 6.1) allowed location of the remaining non-hydrogen atoms.

Ultrene® 99 dicyclopentadiene (DCPD) was obtained from Cymetech Corporation. A modified DCPD base resin containing 20-25% tricyclopentadiene (and small amounts of higher cyclopentadiene homologs) (DCPD-HT) was prepared by heat treatment of Ultrene® 99 DCPD generally as described in U.S. Pat. No. 4,899,005.

Catalysts C931, C933, C793, C827, C705, C727, C748, and C848 were prepared using known methods.

¹H and ¹³C NMR spectra were recorded on a Varian 400 MHz spectrometer. Chemical shifts are reported in ppm downfield from Me₄Si by using the residual solvent peak as an internal standard (CDCl₃δ 7.24 ppm). Spectra were analyzed and processed using MestReNova software.

General GC method conditions: injection temperature, 250° C.; detector temperature, 280° C.; oven temperature, starting temperature, 100° C.; hold time, 1 min. The ramp rate was 10° C./min to 250° C., hold time 12 min; carrier gas helium.

GC Method 1: Column: DB-225, 30 m×0.25 mm (ID)×0.25 μm film thickness. Manufacturer: Agilent; GC and column conditions: Injector temperature: 220° C., Detector temperature: 220° C.; Oven temperature: Starting temperature: 35° C., hold time: 0.5 minutes.

Ramp rate 10° C./min to 130° C., hold time: 0 minutes. Ramp rate 20° C./min to 220° C., hold time: 5 minutes. Carrier gas: Helium. Mean gas velocity: 25 cm/sec. Split ratio: 20:1.

The following abbreviations are used in the examples:

mL milliliter

DCM/CH₂Cl₂ dichloromethane

C₆D₆ deuterated benzene

CDCl₃ deuterated chloroform

CD₂Cl₂ deuterated dichloromethane

C931

-   [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro     (phenylindenylidene) (triphenylphosphine)ruthenium(II) -   [CAS 340810-50-6]     C793

-   [1,3-Bis(2-methylphenyl)-2-imidazolidinylidene]dichloro(benzylidene)     (tricyclohexylphosphine)ruthenium(II) -   [CAS 927429-60-5]     C827

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)     (tricyclohexylphosphine)ruthenium(II) -   [CAS 253688-91-4]     C933

-   Dichloro[1,3-bis(2,6-di-iso-propylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)     ruthenium(II) -   [CAS 373640-75-6]     C848

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(tricyclohexylphosphine)     ruthenium(II) -   [CAS 246047-72-3]     C748

-   [1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(3-phenyl-1H-inden-1-ylidene)(pyridyl)ruthenium     (II) -   [CAS 1031262-76-6]     C727

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](benzylidene)(dipyridine)     ruthenium(II) -   [CAS 357186-58-4]     C705

-   Dichloro[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene](3-methyl-2-butenylidene)(dipyridine)ruthenium(II) -   [CAS 507274-22-8]     DMSO dimethylsulfoxide     PCy₃ tricyclohexylphosphine     EtOAc ethylacetate     MTBE methyl tert-butyl ether     THF tetrahydrofuran     CHP cumene hydroperoxide     5C14 5-tetradecene     5C10 5-decene     9C18 9-octadecene

EXAMPLES Example 1 Synthesis of C747

To a 20 mL scintillation vial equipped with a magnetic stir bar were added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.268 mmol), dimethyl sulfoxide (0.210 g, 2.68 mmol), and dichloromethane (4 mL). The reaction was stirred for one hour then filtered through a plug of celite and combined with diethyl ether (30 mL). The resulting black precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) then dried in vacuum to afford C747 as a black powder (0.346 g, 86.3% yield). The X-ray structure of C747 is shown in FIG. 1.

¹H NMR (400 MHz, CDCl₃): δ 8.68 (d, J=7.4 Hz, 1H), 7.71 (d, J=7.6 Hz, 2H), 7.52 (t, J=7.1 Hz, 1H), 7.42 (t, J=7.5 Hz, 2H), 7.31 (t, J=7.4 Hz, 1H), 7.25 (t, J=7.1 Hz, 1H), 7.11 (d, J=6.1 Hz, 2H), 7.04 (d, J=7.0 Hz, 1H), 6.86 (s, 1H), 6.26 (d, J=3.8 Hz, 2H), 4.13-3.99 (m, 1H), 3.99-3.80 (m, 2H), 3.80-3.69 (m, 1H), 2.82 (s, 3H), 2.69 (s, 3H), 2.68 (s, 3H), 2.41 (s, 3H), 2.35 (s, 3H), 2.11 (s, 3H), 2.05 (s, 3H), 1.77 (s, 3H).

Example 2 Synthesis of C647_(m)

To a 40 mL scintillation vial equipped with a magnetic stir bar were added C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g, 0.30 mmol), dimethyl sulfoxide (0.230 g, 2.94 mmol), and dichloromethane (4 mL). The reaction was stirred at ambient temperature for one hour then filtered through a plug of celite and combined with diethyl ether (30 mL). The resulting purple precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) then dried in vacuum to afford C647_(m) as a purple crystalline solid (0.269 g, 70.7% yield). The X-ray structure of C647_(m) is shown in FIG. 2.

¹H NMR (400 MHz, C₆D₆) δ 16.03 (s, 1H), 8.15 (d, J=25.0 Hz, 2H), 7.21 (t, J=7.3 Hz, 1H), 7.00 (t, J=7.8 Hz, 2H), 6.84 (s, 1H), 6.75 (s, 1H), 6.65 (s, 1H), 6.17 (s, 1H), 3.33-3.00 (m, 4H), 2.87 (s, 3H), 2.67 (s, 3H), 2.61 (s, 3H), 2.22 (s, 3H), 2.14 (s, 3H), 2.07 (s, 3H), 2.04 (s, 3H), 1.98 (s, 3H).

Example 3 Synthesis of C731

To a 40 mL scintillation vial equipped with a magnetic stir bar were added C933 (0.500 g, 0.536 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), dimethyl sulfoxide (0.209 g, 2.68 mmol), and ethyl acetate (10 mL). The reaction was stirred at ambient temperature for three hours affording a fine blue-gray precipitate. The solid was isolated by filtration, washed with ethyl acetate (2×5 mL) then dried in vacuum to afford C731 as a blue-gray solid (0.148 g, 37.8% yield).

¹H NMR (400 MHz, C₆D₆): δ 16.16 (s, 1H), 7.99 (s, 2H), 7.31-7.01 (m, 6H), 6.94 (t, J=7.2 Hz, 2H), 6.65 (d, J=7.2 Hz, 1H), 4.63-4.48 (m, 1H), 4.07-3.92 (m, 1H), 3.76-3.60 (m, 2H), 3.60-3.44 (m, 3H), 3.42-3.27 (m, 1H), 1.97 (s, 3H), 1.87 (d, J=6.0 Hz, 3H), 1.72 (s, 3H), 1.67 (d, J=6.7 Hz, 3H), 1.65 (d, J=6.8 Hz, 3H), 1.20 (d, J=6.3 Hz, 3H), 1.12 (d, J=6.3 Hz, 3H), 1.04 (d, J=6.1 Hz, 3H), 0.88 (d, J=6.5 Hz, 3H), 0.77 (d, J=5.7 Hz, 3H).

Example 4 Synthesis of C591

To a 40 mL scintillation vial equipped with a magnetic stir bar were added C793 (0.500 g, 0.631 mmol), p-toluenesulfonyl chloride (0.060 g, 0.32 mmol), dimethyl sulfoxide (0.246 g, 3.15 mmol), and methyl tert-butyl ether (10 mL). The reaction was stirred at ambient temperature for four hours affording a purple precipitate. The solid was isolated by filtration then recrystallized from dichloromethane and diethyl ether. The resulting purple crystals were isolated by filtration, washed with diethyl ether (2×5 mL) then dried in vacuum to afford C591 as a purple crystalline solid (0.234 g, 62.7% yield). Two isomers [87:13], which are not stereoisomers, were observed in solution.

¹H NMR (400 MHz, CD₂Cl₂, major isomer) δ 15.82 (s, 1H), 8.72 (d, J=7.7 Hz, 1H), 7.78 (d, J=7.5 Hz, 2H), 7.56 (dd, J=16.6, 8.1 Hz, 2H), 7.52-7.39 (m, 2H), 7.24 (t, J=7.9 Hz, 3H), 7.15 (d, J=7.9 Hz, 1H), 6.96 (t, J=7.5 Hz, 1H), 6.45 (t, J=7.6 Hz, 1H), 4.59-4.47 (m, 1H), 4.22 (q, J=10.1 Hz, 1H), 3.90 (q, J=10.4 Hz, 1H), 3.83-3.72 (m, 1H), 2.67 (s, 3H), 2.59 (s, 3H), 2.29 (s, 3H), 1.90 (s, 3H).

¹H NMR (400 MHz, CD₂Cl₂, minor isomer, selected resonances) δ 16.02 (s, 1H), 8.91 (d, J=7.7 Hz, 1H), 7.73 (d, J=7.6 Hz, 3H), 6.90-6.84 (m, 1H), 4.43-4.34 (m, 1H), 2.40 (s, 3H), 2.01 (s, 3H), 1.96 (s, 3H).

Example 5 Synthesis of C625

To a 40 mL scintillation vial equipped with a magnetic stir bar were added C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g, 0.30 mmol), dimethyl sulfoxide (0.236 g, 3.02 mmol), and methyl tert-butyl ether (10 mL). The reaction was stirred at ambient temperature for twenty four hours and the resulting brown precipitate was isolated by filtration, washed with methyl tert-butyl ether (2×10 mL) then dried in vacuum to afford C625 as a light brown solid (0.298 g, 78.8% yield).

¹H NMR (400 MHz, CDCl₃) δ 16.10 (d, J=11.3 Hz, 1H), 7.83 (d, J=11.2 Hz, 1H), 7.08 (s, 1H), 7.05 (s, 1H), 6.82 (s, 1H), 6.73 (s, 1H), 4.13-4.00 (m, 1H), 4.00-3.78 (m, 3H), 2.73 (s, 6H), 2.55 (s, 3H), 2.54 (s, 3H), 2.38 (s, 3H), 2.32 (s, 3H), 2.22 (s, 6H), 1.33 (s, 3H), 1.27 (s, 3H).

Example 6 Synthesis of C865

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), and toluene (5 mL). The reaction was stirred at ambient temperature for two hours then diluted with diethyl ether (15 mL). The precipitate was isolated by filtration, washed with diethyl ether (2×20 mL) followed by hexanes (1×20 mL) then dried in vacuum to afford C865 (0.418 g, 90.0% yield).

¹H NMR (400 MHz, CDCl₃) δ 8.72 (d, J=7.2 Hz, 1H), 7.71 (d, J=7.7 Hz, 2H), 7.52 (t, J=7.3 Hz, 1H), 7.42 (t, J=7.5 Hz, 2H), 7.33-7.20 (m, 4H), 7.20-7.14 (m, 3H), 7.11 (d, J=8.9 Hz, 2H), 7.04 (d, J=7.0 Hz, 1H), 6.93 (s, 1H), 6.28 (s, 2H), 4.15-4.03 (m, 1H), 4.03-3.86 (m, 2H), 3.84-3.71 (m, 1H), 2.92-2.85 (m, 2H), 2.84 (s, 3H), 2.69 (s, 3H), 2.70-2.60 (m, 1H), 2.43 (s, 3H), 2.36 (s, 3H), 2.35 (s, 3H), 2.09 (s, 3H), 2.15-2.04 (m, 1H), 2.04-1.90 (m, 2H), 1.78 (s, 3H), 1.82-1.73 (m, 2H).

Example 7 Synthesis of C861

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), and ethyl acetate (5 mL). The reaction was stirred at ambient temperature for three hours then diluted with diethyl ether (25 mL). The precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) followed by hexanes (1×20 mL) then dried in vacuum to afford C861 (0.386 g, 83.5% yield).

¹H NMR (400 MHz, CDCl₃) δ 8.71 (d, J=7.2 Hz, 1H), 7.70 (d, J=7.7 Hz, 2H), 7.51 (t, J=7.2 Hz, 1H), 7.41 (t, J=7.4 Hz, 2H), 7.33-7.19 (m, 2H), 7.11 (d, J=8.1 Hz, 2H), 7.03 (d, J=7.1 Hz, 1H), 6.92 (s, 1H), 6.27 (s, 2H), 4.11 (dd, J=14.3, 7.1 Hz, 2H), 4.15-4.02 (m, 1H), 4.03-3.85 (m, 2H), 3.84-3.71 (m, 1H), 2.92-2.79 (m, 2H), 2.83 (s, 3H), 2.68 (s, 3H), 2.70-2.59 (m, 1H), 2.42 (s, 3H), 2.35 (s, 3H), 2.08 (s, 3H), 2.15-2.07 (m, 1H), 2.03 (s, 3H), 2.02-1.90 (m, 2H), 1.77 (s, 3H), 1.82-1.73 (m, 2H), 1.25 (t, J=7.1 Hz, 3H).

Example 8 Synthesis of C773

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), tetrahydrothiophene 1-oxide (0.279 g, 2.68 mmol), and dichloromethane (4 mL). The reaction was stirred at ambient temperature for three hours then diluted with diethyl ether (30 mL). The precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) followed by hexanes (1×20 mL) then dried in vacuum to afford C773 (0.345 g, 83.0% yield).

¹H NMR (400 MHz, CDCl₃) δ 8.71 (d, J=7.1 Hz, 1H), 7.71 (d, J=7.6 Hz, 2H), 7.52 (t, J=7.1 Hz, 1H), 7.42 (t, J=7.4 Hz, 2H), 7.34-7.19 (m, 2H), 7.11 (d, J=8.0 Hz, 2H), 7.03 (d, J=7.0 Hz, 1H), 6.92 (s, 1H), 6.28 (s, 2H), 4.14-4.03 (m, 1H), 4.03-3.86 (m, 2H), 3.82-3.72 (m, 1H), 2.83 (s, 3H), 2.91-2.79 (m, 2H), 2.69 (s, 3H), 2.72-2.60 (m, 1H), 2.42 (s, 3H), 2.36 (s, 3H), 2.18-2.04 (m, 1H), 2.08 (s, 3H). 2.04-1.88 (m, 2H), 1.77 (s, 3H), 1.82-1.73 (m, 2H).

Example 9 Synthesis of C673

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C848 (0.500 g, 0.589 mmol), p-toluenesulfonyl chloride (0.056 g, 0.30 mmol), tetrahydrothiophene 1-oxide (0.307 g, 2.94 mmol), and dichloromethane (4 mL). The reaction was stirred at ambient temperature for one hour then diluted with diethyl ether (25 mL). The precipitate was isolated by filtration, washed with diethyl ether (2×10 mL) followed by hexanes (1×15 mL) then dried in vacuum to afford C673 (0.248 g, 62.6% yield).

¹H NMR (400 MHz, CDCl₃) δ 16.12 (s, 1H), 7.82 (d, J=7.7 Hz, 2H), 7.55 (t, J=7.2 Hz, 1H), 7.23 (t, J=7.7 Hz, 2H), 7.11 (br s, 2H), 6.93 (s, 1H), 6.29 (s, 1H), 4.11-3.94 (m, 3H), 3.86-3.76 (m, 1H), 2.72 (s, 3H), 2.69 (s, 3H), 2.64 (s, 3H), 2.62-2.45 (m, 3H), 2.35 (s, 3H), 2.27-2.17 (m, 1H), 2.15 (s, 3H), 2.07 (s, 3H), 2.05-1.91 (m, 2H), 1.84-1.68 (m, 2H).

Example 10 Synthesis of C651

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C827 (0.500 g, 0.605 mmol), p-toluenesulfonyl chloride (0.058 g, 0.30 mmol), tetrahydrothiophene 1-oxide (0.315 g, 3.02 mmol), and ethyl acetate (5 mL). The reaction was stirred at ambient temperature for 16 hours. The precipitate was isolated by filtration and recrystallized from dichloromethane/methanol at −30° C. The resulting purple crystalline product was isolated by filtration, washed with dichloromethane/methanol (1:10, 2×5 mL) then dried in vacuum to afford C651 (0.141 g, 35.7% yield).

¹H NMR (400 MHz, CDCl₃) δ 16.73 (d, J=11.3 Hz, 1H), 7.66 (d, J=11.5 Hz, 1H), 7.09 (s, 1H), 7.05 (s, 1H), 6.83 (s, 1H), 6.71 (s, 1H), 4.17-4.02 (m, 1H), 4.01-3.84 (m, 3H), 3.16-3.06 (m, 1H), 3.02-2.89 (m, 1H), 2.85-2.74 (m, 2H), 2.75 (s, 3H), 2.59 (s, 3H), 2.54 (s, 3H), 2.33 (s, 6H), 2.22 (s, 3H), 2.14-2.02 (m, 2H), 1.99-1.83 (m, 2H), 1.34 (s, 3H), 1.26 (s, 3H).

Example 11 Synthesis of C831_(m)

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C931 (0.500 g, 0.537 mmol), p-toluenesulfonyl chloride (0.051 g, 0.27 mmol), dibutyl sulfoxide (0.436 g, 2.69 mmol), and diethyl ether (10 mL). The reaction was stirred at ambient temperature for twelve hours. The precipitate was isolated by filtration, washed with diethyl ether (1×10 mL) followed by hexanes (1×20 mL) then dried in vacuum to afford C831_(m) (0.195 g, 43.7% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 8.68-8.60 (m, 1H), 7.77-7.69 (m, 2H), 7.57-7.50 (m, 1H), 7.44 (t, J=7.5 Hz, 2H), 7.35-7.28 (m, 2H), 7.15 (s, 1H), 7.13 (dd, J=5.6, 2.7 Hz, 1H), 7.07 (s, 1H), 6.77 (s, 1H), 6.36 (s, 1H), 6.21 (s, 1H), 4.06-3.95 (m, 1H), 3.94-3.81 (m, 2H), 3.78-3.65 (m, 1H), 2.94 (ddd, J=14.5, 12.3, 5.6 Hz, 1H), 2.77 (s, 3H), 2.70 (s, 3H), 2.64-2.51 (m, 1H), 2.47 (s, 3H), 2.36 (s, 3H), 1.95 (s, 3H), 1.73 (s, 3H), 1.71-1.60 (m, 1H), 1.60-1.43 (m, 2H), 1.33-1.19 (m, 2H), 1.19-1.03 (m, 2H), 0.98-0.91 (m, 2H), 0.88 (t, J=7.2 Hz, 3H), 0.83-0.70 (m, 1H), 0.48 (t, J=7.3 Hz, 3H).

Example 12 Synthesis of C885_(ss)

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C747 (0.590 g, 0.790 mmol), (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine)zinc(II) (0.291 g, 0.869 mmol), and tetrahydrofuran (8 mL). The reaction was stirred at ambient temperature for one hour then concentrated to dryness. The resulting residue was extracted with dichloromethane (10 mL), filtered through a plug of celite, and then concentrated in vacuum to about 5 mL. Slow addition of hexanes (30 mL) with rapid stirring afforded a precipitate that was isolated by filtration, washed with hexanes (2×10 mL) then dried in vacuum to afford C885_(ss ()0.604 g, 86.4% yield) as a dark purple powder.

¹H NMR (400 MHz, CD₂Cl₂) δ 7.76 (d, J=7.3 Hz, 2H), 7.55-7.40 (m, 3H), 7.31 (br s, 1H), 7.20 (br s, 1H), 7.12 (br s, 1H), 7.04 (t, J=7.3 Hz, 2H), 6.97 (d, J=6.7 Hz, 1H), 6.84 (br s, 1H), 6.74 (t, J=7.2 Hz, 1H), 6.31 (d, J=7.6 Hz, 2H), 6.19 (br s, 1H), 4.03 (br s, 1H), 3.92 (br s, 3H), 2.90 (br s, 3H), 2.64 (br s, 3H), 2.43 (br s, 6H), 2.26 (br s, 6H), 2.18 (br s, 3H), 1.78 (br s, 3H).

Example 13 Synthesis of C785_(ss)

To a 40 mL scintillation vial equipped with a magnetic stir bar was added C647 (0.300 g, 0.464 mmol), (3,6-dichlorobenzene-1,2-dithiolato)(ethylenediamine) zinc(II) (0.171 g, 0.510 mmol), and tetrahydrofuran (5 mL). The reaction was stirred at ambient temperature for thirty minutes then concentrated to dryness. The resulting residue was extracted with dichloromethane (20 mL), passed through a 0.2 μm syringe filter, and then concentrated in vacuum to ca. 4 mL. Diethyl ether (30 mL) was added slowly affording a green microcrystalline precipitate. The product was isolated by filtration, washed with diethyl ether (2×5 mL) and dried in vacuum to afford C785_(ss) (0.283 g, 77.8% yield).

¹H NMR (400 MHz, CD₂Cl₂) δ 14.77 (s, 1H), 7.28 (t, J=7.3 Hz, 1H), 7.18 (d, J=8.1 Hz, 1H), 7.10 (d, J=8.2 Hz, 1H), 7.06 (s, 1H), 6.90-6.81 (m, 4H), 6.47 (d, J=7.3 Hz, 2H), 6.23 (s, 1H), 4.10-3.90 (m, 4H), 2.71 (s, 3H), 2.68 (s, 3H), 2.66 (s, 3H), 2.35 (s, 3H), 2.30 (s, 3H), 2.28 (s, 3H), 2.21 (s, 3H), 2.02 (s, 3H).

Synthesis of Second Generation Grubbs Ruthenium Olefin Metathesis Catalysts Example 14 Synthesis of C947 from C747

To a 20 mL scintillation vial equipped with a magnetic stir bar were added C747 (0.500 g, 0.670 mmol), (PhO)PPh₂ ([CAS 13360-92-4] 0.196 g, 0.703 mmol), and dichloromethane (5 mL). The reaction was stirred at ambient temperature for one hour then concentrated to 1 mL under vacuum. Hexanes (14 mL) was added and the resulting precipitate was isolated by filtration, washed with hexanes (2×10 mL) then dried in vacuum to afford C947 as a red-brown powder (0.599 g, 94.5% yield). The ¹H NMR data correspond to the data found in the literature.

Example 15 Synthesis of C627 from C747

To a 20 mL scintillation vial equipped with a magnetic stir bar were added C747 (0.500 g, 0.670 mmol), 2-isopropoxy-β-methylstyrene (0.153 g, 0.870 mmol), heptanes (5 mL), and methanol (1 mL). The reaction was stirred at 60° C. for two hours then cooled to ambient temperature. The resulting precipitate was isolated by filtration, washed with methanol (2×5 mL) then dried in vacuum to afford C627 as a green solid (0.332 g, 79.1% yield). The ¹H NMR data correspond to the data found in the literature.

Example 16 Synthesis of C627 from C647_(m)

To a 20 mL scintillation vial equipped with a magnetic stir bar were added C647m (0.400 g, 0.619 mmol), 2-isopropoxy-P-methylstyrene (0.142 g, 0.804 mmol), heptanes (5 mL), and methanol (1 mL). The reaction was stirred at 60° C. for one hour then cooled to ambient temperature. The resulting precipitate was isolated by filtration, washed with methanol (2×5 mL) then dried in vacuum to afford C627 as a green solid (0.228 g, 58.9% yield). The ¹H NMR data correspond to the data found in the literature.

Example 17 Synthesis of C848 from C747

To a 20 mL scintillation vial was added C747 (0.300 g, 0.402 mmol), internal olefin [stilbene or β-methylstyrene] (3.6-10 equiv), and halogenated solvent (chloroform or dichloromethane, 4 mL). Reactions were heated at 40 or 60° C. with stirring until <5% C747 remained as determined by ¹H NMR spectroscopy (2 to 24 hours). PCy₃ (0.124 g, 0.442 mmol) was subsequently added and the reaction stirred for an additional 30 minutes. Yields of C848 ranged from 50-80% as judged by ¹H and ³¹P NMR spectroscopy. The ¹H NMR data correspond to the data found in the literature.

Catalytic Activity of the Olefin Metathesis Catalysts of the Invention Example 18 ROMP Reaction of DCPD-HT

The catalytic activity of the complexes according to the invention was evaluated in ROMP reactions as follows. A 250 mL beaker was filled with 100 g of DCPD-HT monomer and 50 ppm of CHP. The monomer was equilibrated to the desired temperature in an oil bath (30° C.+/−0.5° C.). A J-Type thermocouple was suspended directly into the center of the monomer. The catalyst under study was dissolved in solvent (either toluene or CH₂Cl₂) to form a catalyst solution and the catalyst solution was then added to the monomer at a molar ratio of 45,000:1 (monomer:catalyst) to form a ROMP composition. Addition of the catalyst to the monomer to form the ROMP composition denoted the start of the ROMP reaction and hence, this was time point zero. Temperature readings were recorded using the thermocouple. The exotherm time was determined by measuring the amount of time that passed (i.e., the time difference) between time point zero and the time point that a propagating interface of the ROMP composition was first visually observed as the ROMP composition transitioned from a liquid state or gel state to a cured polymer state. ROMP reactions were stopped 2 hours after addition of the catalyst solution to the monomer. Time to exotherm is expressed by: slow>120 minutes; moderate 30-120 minutes; medium 1-<30 minutes; fast<1 minute and peak exotherm temperature. The results are shown in Table (5).

TABLE (5) DCPD-HT Monomer Peak Exotherm Catalyst Temperature (° C.) Temperature (° C.) Time to Exotherm C647_(m) 30 186 medium C861 30 190 medium C865 30 188 medium C773 30 188 medium C673 30 188 medium C625 30 190 fast C651 30 192 moderate C731 30 171 slow C591 30 167 moderate

Example 19 RCM of Diethyl-2,2-diallylmalonate

Following the procedure outlined in Organometallics, 2006, 25, 5740-5745, inside an argon filled glovebox, a screwcap NMR tube fitted with a PTFE septum was charged with CD₂C₁₂ (0.75 mL or 0.775 mL) and catalyst stock solution (0.016 M, 50 μL, 0.80 μmol, 1.0 mol % or 0.016 M, 25 μL, 0.80 μmol, 0.5 mol %). Samples were equilibrated to 30° C. in a preheated NMR probe before diethyl 2,2-diallylmalonate (19.3 μL, 19.2 mg, 0.080 mmol, 0.1 M) was added via syringe. The ensuing reaction was monitored for 30 minutes using the Varian array function and the conversion to diethyl cyclopent-3-ene-1,1-dicarboxylate was determined by comparing the ratio of the integrals of the methylene protons in the starting material, δ 2.61 (dt), with those in the product, δ 2.98 (s). FIG. 3 shows the conversion of diethyl 2,2-diallylmalonate to 4,4-bis(ethoxy carbonyl)cyclopentene, wherein Catalyst is: C747, C748, C647, C773, C625, C727, or C705.

Example 20 Self-Metathesis of cis-5-Tetradecene (5C14)

In an argon filled glovebox, a 4 mL scintillation vial equipped with a magnetic stir bar was charged with C785ss (0.0046 g, 0.0059 mmol) and tetrahydrofuran (0.5 mL). cis-5-Tetradecene (0.150 mL total, 0.588 mmol) was subsequently added, the vial was sealed and stirred at 40° C. The reaction was sampled at appropriate time intervals and yields/stereoselectivies were determined by gas chromatography (Method 1) as shown in Table (6).

TABLE (6) 5C14 5C10 9C18 9C18 time (h) yield (%) yield (%) yield (%) (Z/E) 1 50 24 25 93/7 2 50 24 24 92/8 

What is claimed is:
 1. An olefin metathesis catalyst selected from:


2. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C763, C663, or C641.
 3. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C773, C673, C651.
 4. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C831_(m).
 5. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C625 or C641.
 6. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C763, C747, or C773.
 7. The olefin metathesis catalyst according to claim 1, wherein the catalyst is C591, C731, C647, C647, C676, or C673. 